CN105948084A - Method for producing magnesium sulfate monohydrate with copper tailings taken as raw material - Google Patents
Method for producing magnesium sulfate monohydrate with copper tailings taken as raw material Download PDFInfo
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Abstract
The invention discloses a method for producing magnesium sulfate monohydrate with copper tailings taken as a raw material and belongs to the technical field of resource utilization of tailings. The method comprises steps as follows: the copper tailings and concentrated sulfuric acid are mixed and heated, water is added to immerse an obtained product, and a magnesium-containing immersion liquid and leaching residues are obtained after solid-liquid separation; H2O2 are added to the magnesium-containing immersion liquid, magnesium hydroxide is added to regulate the pH value to 3.3-3.5, filtration is performed, and a magnesium-rich filtrate is obtained; anhydrous magnesium sulfate is added to the magnesium-rich filtrate, the mixture is stirred and left to stand, and crystals are separated out; a crystallized mother liquid and hydrous magnesium sulfate are obtained through solid-liquid separation, the hydrous magnesium sulfate crystals are dried, and magnesium sulfate monohydrate is obtained; the crystallized mother liquid is returned to the magnesium-rich filtrate to promote crystallization of the magnesium-rich filtrate; the copper tailings contain silicon, magnesium and iron, the mass percentage of magnesium in the copper tailings is larger than 17%. According to the method for producing magnesium sulfate monohydrate with the copper tailings taken as the raw material, the purity and the yield of magnesium sulfate monohydrate can be effectively increased, impurities such as iron and the like are removed and recovered, the production cost is low, the efficiency is high, and pollution is avoided.
Description
Technical field
The present invention relates to a kind of method being raw material production magnesium sulfate monohydrate with copper tailing, belong to Making Use of Tailings and utilize technical field.
Background technology
Copper tailing, also known as copper tailings, the rear remaining fine powder grains of sand size-reduced by Ore, selected form.The primary copper ore resource contrast pole of China lacks, but copper tailing secondary resource amount is the biggest.According to statistics, between 2007, whole nation copper tailing discharge is about 2,400,000,000, and year quantum of output is in the trend increased year by year.The composition of copper tailing wherein copper content 0.3%, silver is 30 grams/per ton, zinc accounts for 0.35%, lead is 0.6%, mineralogical composition mainly has calcite, plagioclase, diopside, hornblend, Actinolitum, garnet, Chalkopyrite, quartz, chlorite, magnetic Ore, magnetic iron ore etc., belongs to aluminosilicate salt form mine tailing.
Applicant finds under study for action, existing copper tailing is dealt with improperly, can bring bigger harm: the most conventional tailings processing method is to set up Tailings Dam, carries out the mine tailing of generation piling up storage, this processing mode easily produces a lot of problem, not only occupy land resource, and, after mine tailing is corroded by the external world, heavy metal element therein can migrate in air and water and soil, cause serious environmental pollution, additionally, Tailings Dam exists the potential hazard of dam break.Goaf filling and to be used as construction material etc. be also a kind of effective way directly utilizing mine tailing.But this Land use systems wastes substantial amounts of valuable element in mine tailing.From the thinking of Developing Mining Recycling Economy, the higher value application of copper tailing is extremely urgent.Recovery barite from copper tailing is studied by Liu Sanjun etc., it is thus achieved that barium sulfate grade is the barite of 91.68%.Technology of Anqing from cupric 0.119%, iron content 11% mine tailing reclaimed copper and iron resource.Mu Xiaohui uses the sorting process of floatation desulphurization-weak magnetic separation iron-reverse flotation fall silicon with certain nominal group process for raw material, has obtained iron ore concentrate and the iron concentrate of sulfur grade 36.42% of Iron grade 66.82%.Du Shuhua develops valuable metal copper, sulfur, gold, silver, ferrum gradient successively preferential separating technology associating new method in copper tailing, acquisition copper acquisition copper, sulfur, iron concentrate grade are respectively 17.62%, 41.75% and 63.28%, the response rate is respectively 49.80%, 78.94% and 21.18%, wherein copper concentrate is containing gold 24.49g/t, gold recovery 40.82%；Argentiferous 260.10g/t, the response rate 22.77%, iron concentrate argentiferous 30g/t, silver raising recovery rate 21.92%, the accumulative response rate 44.69% of silver.Applicant finds under study for action, although prior art exists following defect: the most relatively low firstly for the recovery purity of metallic element in copper tailing, the response rate, secondly, preferable recovery method is not had for the element magnesium in copper tailing, as used existing magnesium sulfate monohydrate extracting method to reclaim the magnesium in copper tailing, the purity of gained magnesium is low, the response rate is low and contains the impurity of other elements more.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, a kind of method being raw material production magnesium sulfate monohydrate with copper tailing is provided, the method can be effectively improved purity and the yield of magnesium sulfate monohydrate, remove ferrum element class impurity and recycle, production cost is low, efficiency is high, pollution-free.
The technical solution adopted for the present invention to solve the technical problems is: the method that should be raw material production magnesium sulfate monohydrate with copper tailing, it is characterised in that comprise the following steps:
1) copper tailing is mixed with concentrated sulphuric acid 1 ~ 3:1 in mass ratio, be heated to 100 ~ 250 DEG C, constant temperature 1 ~ 3h；
2) step 1) products therefrom is soaked, extraction temperature 60 ~ 80 DEG C, extraction time 2 ~ 4h, obtain containing magnesium immersion and leached mud through solid-liquid separation；
3) under the conditions of temperature 5 ~ 30 DEG C, to containing magnesium immersion adds H2O2Stirring evenly, addition magnesium hydroxide regulation solution ph, to 3.3 ~ 3.5, filters and removes insoluble matter, be filtrated to get rich magnesium filtrate；
4) at temperature 5 ~ 25 DEG C, in rich magnesium filtrate, add anhydrous magnesium sulfate, stir, stand promotion rich magnesium filtrate precipitation aqueous sulfuric acid magnesium crystal；
5) step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, aqueous sulfuric acid magnesium crystal is dried acquisition magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize；
Described copper tailing comprises silicon, magnesium and ferrum, wherein in copper tailing mass percent shared by magnesium more than 17 %.
In described copper tailing used, the mass percent shared by magnesium is 20 ~ 30 %.
The mass percent concentration of described concentrated sulphuric acid is 92% ~ 98%.
The concrete operations of step 1) are: according to copper tailing and concentrated sulphuric acid 1:1 in mass ratio, in copper tailing, the speed with 10ml/min adds concentrated sulphuric acid, is heated to 250 DEG C, heat time heating time 3h.
Described copper tailing comprises element manganese, also includes between step 3) and step 4) operating as follows: in step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese.
Anhydrous magnesium sulfate addition described in step 4) is 1 ~ 2g.
The concrete operations of the stirring described in step 4) are: speed of agitator 10r/min, mixing time 1 ~ 2h.
The concrete operations being dried described in step 5) are: at 250 ~ 300 DEG C, aqueous sulfuric acid magnesium crystal is dried 4 ~ 10h.
The concrete operations being dried described in step 5) are: by aqueous sulfuric acid magnesium crystal at 250 DEG C of dry 10h.
Mass percent 10 ~ 20 % shared by ferrum in described copper tailing.
Applicant is described as follows for preparation method of the present invention:
Applicant finds under study for action, and in copper tailing, ferrum is that content is more, and the element of more difficult removing, and ferrum element can effectively be recycled in step 3) by applicant, thus defines and comprises silicon, magnesium and ferrum in copper tailing.Applicant defines in copper tailing that the mass percent shared by magnesium is more than 17 %, its effect is: when in copper tailing, the content of magnesium is less than 17 %, the cost recovery of magnesium sulfate monohydrate is too high, it not quite reasonable from the point of view of economically, and content of magnesium is the lowest, the magnesium sulfate monohydrate purity prepared can decrease, and causes its added value to reduce.In preferred copper tailing, the mass percent shared by magnesium is 20 ~ 30
%, this content is to produce the value that magnesium sulfate monohydrate is proper from copper tailing, and in copper tailing, the content of magnesium is typically not over 30%.After copper tailing containing magnesium 20 ~ 30 % uses the method for the present invention to extract, the yield of gained magnesium sulfate monohydrate is relatively big, has higher economic benefit.In copper tailing, silicon, magnesium, ferrum are presented in its oxide, step 2) gained leached mud is mainly composed of silicon dioxide, construction material can be used as after reclaiming.
Applicant's mass percent concentration of concentrated sulphuric acid used in step 1) is 92% ~ 98%.Known concentrated sulphuric acid refers to the mass percent concentration sulphuric acid more than 70%.But applicant finds under study for action, when reacting with copper tailing: when concentrated sulphuric acid is less than 92%, the leaching rate of magnesium can be caused to reduce, thus cause degradation harmful effect under the response rate of magnesium；When concentrated sulphuric acid is more than 98%, concentrated sulphuric acid raw material is difficult to obtain.Therefore, the concentrated sulphuric acid using mass percent concentration to be 92% ~ 98% reacts with copper tailing, it is possible to realize optimization in terms of technology, economy and environmental benefit.
Applicant's copper tailing in step 1) adds with concentrated sulphuric acid 1 ~ 3:1 in mass ratio, this scope is based on the combined factors such as content and the sulfuric acid concentration of magnesium in copper tailing and determines, when content of magnesium is in low value in the range of it, copper tailing can be high with the mass ratio of concentrated sulphuric acid, on the contrary, content of magnesium in the range of it at a high value time, copper tailing can be lower with the mass ratio of concentrated sulphuric acid, this is because: (1) in the reasonable scope, both can at utmost leach the magnesium in copper tailing, not result in again the waste of concentrated sulphuric acid.(2) concentrated sulphuric acid amount is excessive, easily leaches other impurity composition in copper tailing, and can increase the remove impurity difficulty of follow-up leachate, affects the quality of magnesium sulfate monohydrate.
Applicant is " in copper tailing, the speed with 10ml/min adds concentrated sulphuric acid, is heated to 100 ~ 250 DEG C, constant temperature 1 ~ 3h " in step 1).It is owing to temperature is to affect an important parameter of chemical reaction, this slaking reaction is the endothermic reaction, heat up and be conducive to reaction to carry out to positive direction, the magnesium in copper tailing is made at utmost to be converted into magnesium sulfate, but the too high volatilization easily causing sulphuric acid of temperature, indirectly reduce sulphuric acid and participate in the concentration of reaction, can reduce the conversion ratio of magnesium, and temperature is too high can increase energy consumption.On the contrary, the too low speed that can reduce reaction of temperature, cause the production cycle elongated.
Applicant is in step 2) middle design extraction temperature 60 ~ 80 DEG C, extraction time 2 ~ 4h's.Extraction temperature rate constant and temperature exponentially relation, properly increase extraction temperature to be conducive to improving leaching velocity and leaching rate, raise owing to the dissolubility of magnesium sulfate can raise along with temperature in the range of 30-80 DEG C, continue to rise high-temperature, the dissolubility of magnesium sulfate can reduce, and therefore this scope is suitable temperature range.Leaching rate extends along with extraction time and improves, but peak value, the long disposal ability that can reduce equipment of extraction time and increase production cost.
Applicant designs addition magnesium hydroxide regulation solution ph to 3.3-3.5 in step 3), in this system, regulate pH value can ensure that ferrum farthest precipitates removing to 3.3-3.5, excessive or too small pH value can cause ferrum to remove not thorough or magnesium precipitate, cause the loss of magnesium, use magnesium hydroxide regulation pH can avoid introducing other impurity.
The effect of step 3) is by containing adding H in magnesium filtrate2O2, by ferrous oxidising for ferric iron, adding magnesium hydroxide regulation solution ph to 3.3 ~ 3.5, ferrum is with Fe (OH)3Precipitation form removes through elimination.When in copper tailing containing manganese element, applicant's design also includes operating as follows between step 3) and step 4): add potassium permanganate in step 3) richness magnesium filtrate and bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese, use above method to remove the manganese element harmful effect to magnesium sulfate monohydrate purity.H in step 3)2O2Excess can be converted into water and oxygen after adding, and will not remain in the solution, and the addition of potassium permanganate can be determined by Fe content in the copper tailing of mensuration.
The mode using crystallize in step 4) obtains the aqueous sulfuric acid magnesium crystal that purity is higher.Owing to the clean liquid of rich magnesium obtained is close to saturated, adding anhydrous magnesium sulfate is all that interpolation 1 ~ 2g can promote its crystallize, applicant adds the reason of 1 ~ 2g anhydrous magnesium sulfate: be owing to anhydrous magnesium sulfate has the characteristic of easily water suction, aqueous magnesium sulfate is become after addition, so there are two benefits: (1) can absorb water a small amount of in filtrate, indirectly serves the effect improving magnesium sulfate concentration, it is to avoid the heating of filtrate concentrates operation, reduce energy consumption, save cost.(2) aqueous magnesium sulfate formed serves the effect of crystal seed, adds the response rate of magnesium sulfate.
Crystalline mother solution is added by step 5) again in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize；Wherein crystalline mother solution can be recycled and reused for the Devitrification step of step 4), even if containing other element impurity in crystalline mother solution, still can obtain highly purified aqueous magnesium sulfate by the way of crystallize.Copper tailing used by the present invention does not contains precious metal gold, silver, may be containing a small amount of copper, step 3) precipitation is except ferrum when, copper strips can be gone out a part, when step 4) crystallization, either temperature or the concentration of copper all do not reach the standard of precipitation simultaneously, copper sulfate separates out it is generally required to the method for evaporation crystallisation by cooling, the purity of magnesium sulfate monohydrate will not be produced impact.
Compared with prior art, a kind of of the present invention is had the beneficial effect that with copper tailing by the method for raw material production magnesium sulfate monohydrate
1, should can be effectively improved purity and the yield of magnesium sulfate monohydrate with the method that copper tailing is raw material production magnesium sulfate monohydrate, and removed ferrum element class impurity and recycle, production cost is low, efficiency is high, pollution-free.
2, can should effectively remove manganese element class impurity with the method method that copper tailing is raw material production magnesium sulfate monohydrate and recycle, improving the purity of magnesium sulfate monohydrate further,
3, the method abundant raw material that should be raw material production magnesium sulfate monohydrate with copper tailing, produces without acid mist, and technique, equipment are simple, reaction condition is easily controllable, the filtering residue obtained can be as the raw material of construction material, and the ferrum of recovery, manganese are recycling, and crystalline mother solution can recycle.
Accompanying drawing explanation
The process chart that Fig. 1 is is raw material production magnesium sulfate monohydrate with copper tailing.
Detailed description of the invention
Embodiment 1 ~ 5 is the detailed description of the invention that the present invention a kind of is the method for raw material production magnesium sulfate monohydrate with copper tailing, and wherein embodiment 1 is most preferred embodiment.In embodiment, firing equipment used by step 1) is Muffle furnace, step 2) and step 5) used by solid-liquid separating equipment be and use vacuum filtration machine.
Embodiment
1
Copper tailing used by the present embodiment comprises the composition of following mass percent: magnesium 30 %, silicon 30%, ferrum 12%, manganese 0.74%.
1) slaking reaction: by 500g copper tailing, joins in reactor, and then the speed with 10ml/min adds the concentrated sulphuric acid of 98%, controls copper tailing and mixes with concentrated sulphuric acid 1:1 in mass ratio, is heated to 250 DEG C, constant temperature 3h；
2) water logging: step 1) products therefrom is soaked, extraction temperature 80 DEG C, extraction time 2h, obtain containing magnesium immersion and leached mud through solid-liquid separation；Leached mud is used as construction material；
3) remove impurity: under the conditions of temperature 5 ~ 30 DEG C, to containing adding H in magnesium immersion2O2Stirring evenly, by ferrous oxidising for ferric iron, add magnesium hydroxide regulation solution ph to 3.5, ferrum is with Fe (OH)3Form form insoluble matter, filter and remove insoluble matter, be filtrated to get rich magnesium filtrate；In step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese；
4) crystallization: at temperature 20 DEG C, adds 1g anhydrous magnesium sulfate, speed of agitator 10r/min in rich magnesium filtrate, and mixing time 2h, standing promote that rich magnesium filtrate separates out aqueous sulfuric acid magnesium crystal；
5) it is dried: step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, by aqueous sulfuric acid magnesium crystal at 250 DEG C of dry 10h, it is thus achieved that magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize.
Embodiment
2
Copper tailing used by the present embodiment comprises the composition of following mass percent: magnesium 25 %, silicon 35%, ferrum 13%, manganese 0.70%.
1) slaking reaction: by 500g copper tailing, joins in reactor, and then the speed with 10ml/min adds the concentrated sulphuric acid of 95%, controls copper tailing and mixes with concentrated sulphuric acid 2:1 in mass ratio, is heated to 200 DEG C, constant temperature 2h；
2) water logging: step 1) products therefrom is soaked, extraction temperature 70 DEG C, extraction time 3h, obtain containing magnesium immersion and leached mud through solid-liquid separation；Leached mud is used as construction material；
3) remove impurity: under the conditions of temperature 5 ~ 30 DEG C, to containing adding H in magnesium immersion2O2Stirring evenly, by ferrous oxidising for ferric iron, add magnesium hydroxide regulation solution ph to 3.5, ferrum is with Fe (OH)3Form form insoluble matter, filter and remove insoluble matter, be filtrated to get rich magnesium filtrate；In step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese；
4) crystallization: at temperature 18 DEG C, adds 1.5g anhydrous magnesium sulfate, speed of agitator 10r/min in rich magnesium filtrate, and mixing time 1.5h, standing promote that rich magnesium filtrate separates out aqueous sulfuric acid magnesium crystal；
5) it is dried: step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, by aqueous sulfuric acid magnesium crystal at 280 DEG C of dry 7h, it is thus achieved that magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize.
Embodiment
3
Copper tailing used by the present embodiment comprises the composition of following mass percent: magnesium 20 %, silicon 35%, ferrum 14%, manganese 0.65%.
1) slaking reaction: by 500g copper tailing, joins in reactor, and then the speed with 10ml/min adds the concentrated sulphuric acid of 93%, controls copper tailing and mixes with concentrated sulphuric acid 3:1 in mass ratio, is heated to 150 DEG C, constant temperature 2.5h；
2) water logging: step 1) products therefrom is soaked, extraction temperature 60 DEG C, extraction time 4h, obtain containing magnesium immersion and leached mud through solid-liquid separation；Leached mud is used as construction material；
3) remove impurity: under the conditions of temperature 5 ~ 30 DEG C, to containing adding H in magnesium immersion2O2Stirring evenly, by ferrous oxidising for ferric iron, add magnesium hydroxide regulation solution ph to 3.4, ferrum is with Fe (OH)3Form form insoluble matter, filter and remove insoluble matter, be filtrated to get rich magnesium filtrate；In step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese；
4) crystallization: under the conditions of temperature 15 DEG C, adds 2g anhydrous magnesium sulfate, speed of agitator 10r/min in rich magnesium filtrate, and mixing time 1h, standing promote that rich magnesium filtrate separates out aqueous sulfuric acid magnesium crystal；
5) it is dried: step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, by aqueous sulfuric acid magnesium crystal at 300 DEG C of dry 5h, it is thus achieved that magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize.
Embodiment
4
Copper tailing used by the present embodiment comprises the composition of following mass percent: magnesium 30 %, silicon 30%, ferrum 18%, without manganese.
1) slaking reaction: by 500g copper tailing, joins in reactor, and then the speed with 15ml/min adds the concentrated sulphuric acid of 92%, controls copper tailing and mixes with concentrated sulphuric acid 1.5:1 in mass ratio, is heated to 100 DEG C, constant temperature 3h；
2) water logging: step 1) products therefrom is soaked, extraction temperature 60 DEG C, extraction time 3h, obtain containing magnesium immersion and leached mud through solid-liquid separation；Leached mud is used as construction material；
3) remove impurity: under the conditions of temperature 5 ~ 30 DEG C, to containing adding H in magnesium immersion2O2Stirring evenly, by ferrous oxidising for ferric iron, add magnesium hydroxide regulation solution ph to 3.4, ferrum is with Fe (OH)3Form form insoluble matter, filter and remove insoluble matter, be filtrated to get rich magnesium filtrate；
4) crystallization: at temperature 15 DEG C, adds 1g anhydrous magnesium sulfate, speed of agitator 10r/min in rich magnesium filtrate, and mixing time 1h, standing promote that rich magnesium filtrate separates out aqueous sulfuric acid magnesium crystal；
5) it is dried: step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, by aqueous sulfuric acid magnesium crystal at 250 DEG C of dry 4h, it is thus achieved that magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize.
Embodiment
5
Copper tailing used by the present embodiment comprises the composition of following mass percent: magnesium 20%, silicon 30%, ferrum 20%, manganese 1%.
1) slaking reaction: by 500g copper tailing, joins in reactor, and then the speed with 10ml/min adds the concentrated sulphuric acid of 98%, controls copper tailing and mixes with concentrated sulphuric acid 1:1 in mass ratio, is heated to 200 DEG C, constant temperature 1h；
2) water logging: step 1) products therefrom is soaked, extraction temperature 60 DEG C, extraction time 2h, obtain containing magnesium immersion and leached mud through solid-liquid separation；
3) remove impurity: under the conditions of temperature 5 ~ 30 DEG C, to containing adding H in magnesium immersion2O2Stirring evenly, by ferrous oxidising for ferric iron, add magnesium hydroxide regulation solution ph to 3.3, ferrum is with Fe (OH)3Form form insoluble matter, filter and remove insoluble matter, be filtrated to get rich magnesium filtrate；In step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese；
4) crystallization: at temperature 17 DEG C, adds 1g anhydrous magnesium sulfate, speed of agitator 10r/min in rich magnesium filtrate, and mixing time 1.5h, standing promote that rich magnesium filtrate separates out aqueous sulfuric acid magnesium crystal；
5) it is dried: step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, by aqueous sulfuric acid magnesium crystal at 300 DEG C of dry 4h, it is thus achieved that magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize.
Performance test
The purity of detection embodiment 1 ~ 5 gained magnesium sulfate monohydrate and the response rate, and typing table 1.
The purity of table 1 embodiment 1 ~ 5 gained magnesium sulfate monohydrate and the response rate
。
Embodiment 1 ~ 5 reaction gained product be step 2) gained leached mud, step 3) gained Fe (OH)3, the insoluble tetravalent manganese of step 3) gained, step 5) gained magnesium sulfate monohydrate, wherein in leached mud, the composition of mass percent more than 98% is silicon dioxide, can serve as construction material, wherein Fe (OH)3, insoluble tetravalent manganese can be with recycling, magnesium sulfate monohydrate is products obtained therefrom.And be can be seen that by table 1, the purity of embodiment 1 ~ 5 gained magnesium sulfate monohydrate and yield all can reach high value.Applicant makes discovery from observation, and embodiment 1 ~ 5 the most all generates without acid mist or irritative gas, and without discharging of waste liquid, environmental protection and economy.
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, and any those skilled in the art are changed possibly also with the technology contents of the disclosure above or are modified as the Equivalent embodiments of equivalent variations.But every without departing from technical solution of the present invention content, any simple modification, equivalent variations and remodeling above example made according to the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. the method that a kind is raw material production magnesium sulfate monohydrate with copper tailing, it is characterised in that comprise the following steps:
1) copper tailing is mixed with concentrated sulphuric acid 1 ~ 3:1 in mass ratio, be heated to 100 ~ 250 DEG C, constant temperature 1 ~ 3h；
2) step 1) products therefrom is soaked in water, extraction temperature 60 ~ 80 DEG C, extraction time 2 ~ 4h, obtain containing magnesium immersion and leached mud through solid-liquid separation；
3) under the conditions of temperature 5 ~ 30 DEG C, to containing magnesium immersion adds H2O2Stirring evenly, addition magnesium hydroxide regulation solution ph, to 3.3 ~ 3.5, filters and removes insoluble matter, be filtrated to get rich magnesium filtrate；
4) at temperature 5 ~ 25 DEG C, in rich magnesium filtrate, add anhydrous magnesium sulfate, stir, stand promotion rich magnesium filtrate precipitation aqueous sulfuric acid magnesium crystal；
5) step 4) richness magnesium filtrate is carried out solid-liquid separation, it is thus achieved that crystalline mother solution and aqueous sulfuric acid magnesium crystal, aqueous sulfuric acid magnesium crystal is dried acquisition magnesium sulfate monohydrate；Crystalline mother solution is added in the rich magnesium filtrate of step 4), promote rich magnesium filtrate crystallize；
Described copper tailing comprises silicon, magnesium and ferrum, wherein in copper tailing mass percent shared by magnesium more than 17 %.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: in described copper tailing used, the mass percent shared by magnesium is 20 ~ 30 %.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: the mass percent concentration of described concentrated sulphuric acid is 92% ~ 98%.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterized in that: the concrete operations of step 1) are: according to copper tailing and concentrated sulphuric acid 1:1 in mass ratio, in copper tailing, the speed with 10ml/min adds concentrated sulphuric acid, be heated to 250 DEG C, heat time heating time 3h.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterized in that: described copper tailing comprises element manganese, also include between step 3) and step 4) operating as follows: in step 3) richness magnesium filtrate, add potassium permanganate bivalent manganese is oxidized to insoluble tetravalent manganese, filter rich magnesium filtrate and remove insoluble tetravalent manganese.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: the anhydrous magnesium sulfate addition described in step 4) is 1 ~ 2g.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: the concrete operations of the stirring described in step 4) are: speed of agitator 10r/min, mixing time 1 ~ 2h.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: described in step 5) be dried concrete operations be: by aqueous sulfuric acid magnesium crystal 250 ~ 300 DEG C be dried 4 ~ 10h.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: described in step 5) be dried concrete operations be: by aqueous sulfuric acid magnesium crystal at 250 DEG C of dry 10h.
The most according to claim 1 a kind of be raw material production magnesium sulfate monohydrate with copper tailing method, it is characterised in that: mass percent 10 ~ 20 % shared by ferrum in described copper tailing.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790290A (en) * | 2019-12-18 | 2020-02-14 | 河南省睿博环境工程技术有限公司 | Method for producing high-purity magnesium sulfate from magnesium-method desulfurization waste residues |
| CN111135773A (en) * | 2020-01-03 | 2020-05-12 | 河北佰斯特药业有限公司 | Method for removing iron and manganese in raw material medicine magnesium sulfate |
| RU2727382C1 (en) * | 2019-11-25 | 2020-07-21 | Акционерное Общество "Группа компаний "Русредмет" (АО "ГК "Русредмет") | Method of producing magnesium sulphate from magnesium-containing raw material |
| CN115432789A (en) * | 2022-08-31 | 2022-12-06 | 中国矿业大学 | Method for preparing ferrous sulfate flocculating agent from copper smelting tailing slag |
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| CN101830475A (en) * | 2010-03-12 | 2010-09-15 | 合肥工业大学 | Method for preparing magnesium silicate and magnesium hydroxide from serpentine or tailings thereof |
| CN104556158A (en) * | 2014-12-25 | 2015-04-29 | 昆明钢铁集团有限责任公司 | Method for preparing calcium sulfate whiskers and magnesium sulfate |
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| CN101830475A (en) * | 2010-03-12 | 2010-09-15 | 合肥工业大学 | Method for preparing magnesium silicate and magnesium hydroxide from serpentine or tailings thereof |
| CN104556158A (en) * | 2014-12-25 | 2015-04-29 | 昆明钢铁集团有限责任公司 | Method for preparing calcium sulfate whiskers and magnesium sulfate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2727382C1 (en) * | 2019-11-25 | 2020-07-21 | Акционерное Общество "Группа компаний "Русредмет" (АО "ГК "Русредмет") | Method of producing magnesium sulphate from magnesium-containing raw material |
| CN110790290A (en) * | 2019-12-18 | 2020-02-14 | 河南省睿博环境工程技术有限公司 | Method for producing high-purity magnesium sulfate from magnesium-method desulfurization waste residues |
| CN111135773A (en) * | 2020-01-03 | 2020-05-12 | 河北佰斯特药业有限公司 | Method for removing iron and manganese in raw material medicine magnesium sulfate |
| CN115432789A (en) * | 2022-08-31 | 2022-12-06 | 中国矿业大学 | Method for preparing ferrous sulfate flocculating agent from copper smelting tailing slag |
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| CN105948084B (en) | 2017-11-24 |
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